Metal containing compositions, processes and products



United States Patent-O This invention; relates to metal containingsanitizing compositions, processes for rendering fibrous materialsdurably microbiocidal with said compositions and the resulting sanitizedproducts, i

It iswell known that certain metals or the salts and other compounds ofthemetals may beapplied to fabrics or other substrates to impart theretomicrobiocidal properties. For example, silver, copper and various othermetal salts have been applied to such materials as fibers, fabrics,animal hides,'paper, wood or the like to protect the base against attackfrom microorganisms, e.g., to make the base material resistant againstmildew, rot, and similar attack by. fungi or bacterial. Many forms ofmetal compositions and processes using these'materials have previouslybeen suggested for accomplishing such results.

The prior known compositions and operations have involved one or morepractical deficiencies. For example, chlorinated phenols, whileinitially effective on fibrous materials, lose their mildewproofing andantibacterial effects when exposed to heat and light or when the treateditem is repeatedly laundered. Quaternary ammonium compounds, whileeffective against selected micro-organisms, do not generally renderfabrics mildew resistant. Moreover, such quaternary compounds whenapplied to fibrous materials lose their antimicrobial activity whenexposed to soaps, detergents and alkaline washing compounds. Coppercontaining compounds, such as copper ncphthenate or copper8-hyd-roxy-quinolate, while effective in rendering cellulosic materialsmildew resistant, are not particularly effective against gram negativeand gram positive organisms. Moreover, when applied to fibrousmaterials, such products require solvent application techniques and alsoproduce a greenish color in the treated article.

It has been previously suggested to treat textile materials with silvernitrate complex salts of ethylene thiourea (see US. Patent 3,061,469).Such treated textile or other fibrous articles, however, Whilepossessing some limited capacity to resist laundering, lose theirantimicrobial effectiveness when exposed to repeated alkaline washingconditions. Further, antimicrobial activity is relatively poor Whentreated fabrics are buried in soil and the complex salts are sensitiveto chlorine upon bleaching to cause a loss of strength when the bleachedfabric is ironed. Moreover, fibrous materials treated with such silverethylene thiOurea compounds become brown colored when washed and exposedto heat and light from the formation of metallic silver or silver oxidedeposits on the treated fibers. Improved biocidal properties in fibroussubstrates have been obtained by impregnation with formaldehydederivatives of silver-'ethyleneurea adducts (see US. Patent 3,085,909).In this case, however, the presence of small amounts of freeformaldehyde may act as a reducing agent for silver and may producefabric discoloration, although durability to multiple washings may beobtained. The potential formation of color in treated articles isgenerally undesirable and more foolproof products or processes have beendemanded by various industries.

A principalv object of this inventionis the provision of new andimproved metal containing compositions 3,300,336 Patented Jan. 24, 1967which may be applied tov fibrous substrates to impart thereto durableand broad range microbiocidal properties without detrimentally affectingthe color characteristics of the treated substrate or without otherwiseadversely affecting the substrate. Further objectsinclude:

(l) The provision of new and improved organometallic compositions thatare effective in rendering fibrous materials resistant to mildew, fungiand rot and at the same time producing microbiocidal andself-sterilizing effects against a wide rangeof gram negative and grampositive organisms as Staphylococcus aureus, E. coli, Chaetomiumglobosum, Trichoderma lignorum, and the like. i

(2) The provision of new compositions which comprise water-soluble orwater-dispersible compounds which can be readily applied to fibrousmaterials through conventional treating techniques to impartmicrobiocidal properties to the fibrous materials v (3) The provisionOfmetal sanitizing compositions which are not discolored, duringstoragejor handling in the treating of, fibrous substrates nor by heator light exposure. I I v i (4) The pro-vision of metal containingcompositions and treating processesutilizing them for impartingmicrobiocidal effects to textiles and other fibrous materials which aredurable enough to withstand repeated laundering, dry cleaning, multiplehigh-temperature alkaline washes or comparable application of cleaningor treating solutions. v

(5) The provision of new metal containing compositions which make itpossible to produce durable rot-proofing on cotton and rayon duck andawning materials, and self-sanitizing effects on diapers,.h ospitalbedding, bed sheets, undergarments and the like and which retain theirstrength despite bleaching and ironing.

(6) The provision of new compositions and methods for producingantiseptic cloth for shoe linings, moldresistant wallpaper,mildew-resistant sailcloth and self sterilizing non-woven fabricfilters.

(7) The provision of new compositions'and methods for reducing rotting.of wood and creating other microbiocidal effects on fibrous substrates.

Other objects and further scope of applicability of the presentinvention will become apparent from the detailed description givenhereinafter; it should be understood, however, that the detaileddescription and specific examples, while indicating preferredembodiments of the invention, are given :by way of illustration only,since various changes and modifications Within the spirit and scope ofthe invention will become apparent to those skilled in the art from thisdetailed description.-

In accordance with the present invention, the organometalliccoordination complex is applied to the textile fabric from a physicaladmixture with a polyfunctional compound or resin capable of reactingwith the -NH- .groups of the complex to form a water-insoluble reactionproduct therewith- In addition to the use of physical mixtures, thepresent invention contemplates a partial prereaction between thecoordination complex and the polyfunctional compound or resin, but theprereaction is a limited one which does not destroy water-dispersibilityso that, upon deposition of the partial reaction product, it is capableof reacting further with the -NH- groups of the complex to form awater-insoluble reaction product therewith. In this way, waterinsolubility is achieved by a polymerization reaction with an agentexternal of the textile being treated providing more extensiveinsolubilization through polymerization; there is no need to form rathercomplex chemicals reacted with both metal salt and formaldehydeand-which are of limited storage stability. and sensitive toformaldehyde release in the immediate vicinity of the metal causingdiscoloration; and the active hydrogen atoms of the NH groups of thecomplex are more completely reacted to provide chlorine-resistantfinishes when the polyfunctional compound or resin is itself resistantto chlorine.

The organo-metallic coordination complexes embraced by the invention arecomplexes of salts of metals having biocidal properties withheterocyclic compound having the formula:

wherein R is a radical selected from the group consisting of hydrogen,hydroxyl and alkyl, alkoxy and :alkoxyalkyl radicals containing from 1-6carbon atoms, and R is selected from the group consisting of a linkingbond and the divalent methylene radical.

The metals which may be used are those having coordination propertiesand these are particularly illustrated by silver, copper, zinc, iron,cadmium, cobalt, chromium, aluminum and nickel. The invention isespecially concerned with silver, copper and zinc, preferably silver.

The organo-metallic coordination complex is conveniently formed bymixing the heterocyclic compound with a salt of the metal in a commonsolvent, especially water,

in a molar ratio of the metal to the heterocyclic com- 1 pound of fromabout 1:1 to 1:10.

The polyfunctional compounds or resins which are employed are thosewhich contain a plurality of functional groups capable of reacting withthe NH- .groups of the complex to form a water-insoluble reactionproduct therewith. This reaction is intended to take place under theinfluence of elevated temperature and after application of thepolyfunctional compound or resin to the textile being treated.Preferably, a functionality of at least 2 is intended tho-ugh higherfunctionality is preferred and somewhat lower functionality down toabout 1.4 may be tolerated.

Various functional groups may be relied upon as indicated below.

Polyepoxides containing the oxirane group illustrated by polyglycidylethers of aromatic or aliphatic polyhydric compounds, such as apolyglycidyl ether of glycerin having an epoxy functionality of about2.3, these being preferred for water dispersibility. Copolymerscontaining the glycidyl group are also useful such as 95/5 copolymer ofethyl acrylate and glycidyl 'methacrylate. While terminal oxirane groupsare preferred for greater reactivity, this is not essential as in thecompound vinyl cyclohexene dioxide.

Polyaldehydes such as dialdehydes and their acetals which release thealdehyde group CHO when heated. Glyoxal is typical of this class ofcompounds.

Polymethylol compounds containing a plurality of -CH OH methylol groups.It will be understood that the methylol group may be etherified with avolatile alcohol, typically methanol, to release the reactivity of themethylol group upon volatilization of the alcohol, and such ethers areembraced within the term methylol. Numerous polymethylol compounds whichare useful are well known, such as polymethylol melamines includingdimethylol melamine, trimethylol melamine, hexamethylol melamine, etc.;dimethylol urea, dimethylol ethylene thiourea, dimethylol ethylene urea,tetramethylol :acetylene, dimethylol 1,3-propylene urea, tetramethylolacetylene diurea, dimethylol N-ethyl triazone, tris methoxymethylmelamine, dimethylol adducts of polyalkylated monoureins (see FrenchPatent 1,318,810), etc.

It should be particularly noted as a feature of the invention thatcompounds containing active hydrogen reactive with chlorine, such asdimethylol urea, do not 4 provide bleach-resistant products and are lesspreferred.

The invention particularly contemplates resinous addition copolymers inwhich the active group is the methylol group and which is essentiallydevoid of active hydrogen reactive with chlorine so that, when the NHgroups of the complex are tied up by the polymerization reaction, theresulting water-insoluble deposit upon the textile material isessentially devoid of groups reactive with chlorine to permit theachievement of superior laundry resistance, color stability,microbiocidal activity, and the capacity to be bleached and then ironedwith relative impunity.

From the standpoint of etherified methylol groups, the preference in theinvention for at least water dispersible materials carries acorresponding preference for lower alcohols, and particularly methanol,as the etherifying agent. While other ether alcohols are fullyoperative, their capacity for water miscibility is lowered with respectto methanol and, hence, these are less preferred.

Still other polyfunctional compounds which may be used are compoundscontaining the ethylene imine group or the aziridinyl group, numerouspolyethylene imine compounds and aziridinyl compounds being known asillustrated by tris aziridinyl phosphine oxides. Reactive quaternaryammonium salts such as those produced by the chloromethylation of amidesand alcohols and having the general formulae:

may also be employed as well as vinyl unsaturated compounds having anactive terminal methylene group such as divinyl sulfones.

The invention is especially directed to compositions which are capableof water application to textile materials and, from this standpoint, thepolyfunctional compound is preferably selected to either possessrelatively low molecular weight or a high degree of functionality (2 ormore and preferably in excess of 2 for cross-linking) in a water solublemoiety in order to achieve the desired properties of water-insolubilityin the reaction product through a thermosetting, cross-linking cure.These materials, which are essentially monomeric, are illustrated bypolymethylol ureas and melamines; polymethoxymethyl ureas and melamines;polymethylol and polymethoxymethyl cyclic ureas, thioureas, andiminoureas; dialdehydes as glyoxal and glutaraldehyde; polyglycidylethers of polyols; tris aziridinyl phosphine oxides and sulfides; andbis quaternaries of chloromethylated glycols.

A second direction of importance is the utilization of relatively highmolecular weight acrylic emulsion copolymers. When these can beformulated in relatively stable aqueous dispersions or emulsion(referred to as latices) they are capable of coreaction with thecomplexes embraced by the invention to provide the desired properties,despite the fact that these emulsion copolymers are linear copolymers.

The copolymers which are especially contemplated are those containing amajor proportion of acrylic ester with a minor proportion, especiallyfrom l25% by weight, of what may be termed a reactive acrylate, the termacrylate embracing derivatives of acrylic acid and methacrylic acid.Still more specifically, the acrylic copolymers which are particularlycontemplated may be identified by the formula:

where: n is fro-m -99% and m is from 251%; R is hydrogen or methyl and Xis a radical containing a group.

which can react with the NH group in the complex. Specific examples ofsuch emulsion copolymers are:

- a copolymer of butyl acrylate and methoxymethyl methacrylamide In theExamples A, B, C and D above, typical values for n and m are 95% and 5%,respectively. These may be prepared as illustrated in United StatesPatentNo.

As will be evident, mixtures of two or more of the polyfunctionalcompounds with the metal coordination complex or mixtures of two or moreof the metal complexes with polyfunctional compounds may be employed.

While application from aqueous medium is preferred as has beenpreviously indicated, it .is also possible to employ the mixtures of theinvention or partial prereaction products thereof in organic solventsolutionor, es-

pecially where the mixture is liquid, as an aerosol.

The preferred aqueous treating compositionsof the invention will containbetween about 0.05 to 5% by weight of the metal-ethylene thioureacomplex, and especially 0.1 to 2% by weight of the complex and 1 to byweight of the .polyfunctional compound, and especially 3 to 10% of thepolyfunctional compound."

Advantageously, the ratio of the metal complex to the polyfunctionalcompound on a weight basis is in the range of from 1:50 to 2:1.

In treating a fibrous substrate such as paper, woven textiles, non-wovenfabrics or the like, between about 0.1 and and, advantageously, 1 to 10%of the combined mixture of metal complex and polyfunctional compoundwill be impregnated in or applied to the'fiber substrate to be treated.Using th'epreferred aqueous solutions or emulsions described, it isadvantageous to control the impregnation or other application of theaqueous composition to give a pick-up of about 50% to 150% by Weightthereof, based upon the weight of the fabric or other fibrous substrateto which the aqueous composition is applied.

6 Advantageously, the treating composition will also contain an acidiccatalyst which will aid in the formation of a water-insoluble,heat-cured reaction product between the metal complex and thepolyfunctional compound. Between about 1- to 10%, based upon the weightof the polyfunctional compound, of the acidic catalyst is preferablyemployed. 7

Following application of the treating composition, the impregnated orotherwise treated fibrous substrate is dried. This is advantageouslyaccomplished by heating to a temperature between about and 150 C. forbetween about 1.10 60minutes.

, To complete the treatment of the fibrous substrates and to convert thereaction product of the metal complex and 'polyfunctional compound intoa heat-cured condition so that the material is durable againstdry-cleaning. laundering or the like, the dried substrate is subjectedto a heatcuring step. Preferably, this is accomplished at a temperaturebetween 100 and 200 C. for about 1 to 60 minutes, longer times generallybeing employed at the lower temperature and viceversa.

A more complete understanding of the new products and methods of thisinvention may be had by reference to the'following working examples ofoperations conducted in accordance with the invention. In these examplesand throughout the remainder of the specification and claims, all partsand percentages are by weight unless otherwise specified.

Example 1 Samples of cotton print cloth were impregnated with about anequal weight of the following solutions, followed by drying for 5minutes at C. and then curing for 5 minutes at 0:

After curing, the two fabrics were laundered up to 25 times in a homeautomatic washer using a synthetic detergent. Then they were tested forantibacterial activity against Staphylococcus aureus using the AATCCTest Method No. 90-1962T, page B-130, 1962 Technical Manual of AATCC.The following results were obtained:

1 1 4 mole ratio of silver nitrate and ethylene thiourea.

Treatment Number Antibacterial Rating and Halo in 111111 Norm-In theabove tabulation,

as well as the further tabulations which follow, the

remarks excellen etc., identify subjective opinion of antibacterialratings and the numerical ratings, such as 1.0, identify the diameter ofthe antibacterial halo measured in millimeters. When the test specimenkills the organism under test in the immediate region of the specimen,but without killing the organism at a distance from the specimen, thespecimen 1 would have a good rating, but it would have a halo of 0millimeter.

Percent Whiteuess Treatment Number Initial 20 Washes Untreated 80 80Solution 1 60 51 Solution 2 80 82 Example 2 Samples of cotton duck weretreated with the solutions given below to give about 100% pick-up,followed by drying for 10 minutes at 120 C. and then curing for 10minutes at 150 C. After curing, they were scoured with a syntheticdetergent in an automatic home washer to remove any unfixed materials.Then the samples were subjected to 14 days soil burial according to TestMethod 5762 of Federal Specifications CCC-T-191b.

Solution 1: Percent Silver-ethylene thiourea nitrate complex, 1:4

mole ratio 0.2 Water 99.8

100.0 Solution 2:

Silver-ethylene thiourea nitrate complex, 1:4

mole ratio 0.2 Dimethylol, N-ethyl triazone 5.0 CatalystMgCl .6H O 1.0Water 93.8

100.0 Solution 3:

Silver-ethylene thiourea nitrate complex, 1:4

mole ratio 0.2 Dimethylol ethylene thiourea 5.0 CatalystMgCl .6H O 1.0Water 93.8

100.0 Solution 4:

Silver-ethylene thiourea nitrate complex, 1:4

mole ratio 0.2 Dimethylol melamine 5.0 CatalystMgCl .6H O 1.0 Water 93.8

100.0 Solution 5:

Copper-ethylene thiourea nitrate complex, 1:4 mole ratio 2.1 Emulsioncopolymer of 95 parts ethyl acrylate and 5 parts N-methylol acrylamide2.5 CatalystNH Cl 0.3 Water 95.1

- 100.0 Solution 6:

Zinc-ethylene thiourea nitrate complex, 1:2 mole ratio 2.3 Emulsioncopolymer of 95 parts ethyl acrylate and 5 parts N-methylol acrylamide2.5 CatalystNH Cl 0.3 Water 94.9

8 Solution 7:

Silver-ethylene thiourea nitrate complex, 1:2 mole ratio 0.2 Emulsioncopolymer of parts ethyl acrylate and 5 parts glycidyl methacrylate 2.5Dimethylol ethylene urea 1.0 Catalyst-0.5% Zn(NO 6H 0 0.5 Water 95.8

The results of the 14 days soil burial test are shown in the tablebelow:

Percent tensile strength Treatment retained after 14 applied days soilburial Untreated control 0 Solution 1 control 0 Solution 2 94 Solution 382 Solution 4 Solution 5 100 Solution 6 95 Solution 7 100 Example 3Samples of cotton fabric were impregnated with about an equal weight ofsolutions of silver-ethylene thiourea nitrate complexes and trismethoxymethyl melamine, followed by drying 5 minutes at C. and thencuring 5 minutes at C; The treating solutions contained:

The treated samples were then given 10 repeated washes with a syntheticdetergent, 10 washes with soap and soda ash, and 10 Washes with soap andsodium hypochlorite bleach. The results of antibacterial tests, aspreviously described, on these specimens are given in the table below.

Antibacterial Rating and Halo in mm.

Treatment Applied 10 Detergent 10 Soap and 10 Soapand Washes Soda Washeshlorme Washes Solution 1 Very good, 0.0... Fair, 00 Excellent, 1.0.Solution 2 Excellent, 0.0...- Good, 0.0. Excellent, 1.0.

Example 4 Samples of cotton fabrics were treated as in Example 1 withvarious solutions containing the metal-ethylene thiourea-acetate complex(1 to 4 mole ratio) and dimethylol ethylene thiourea at a total loadingof 6% solids. The

results of the antibacterial tests are shown in the table below:

Antibacterial Ratings andI-Ialo in mm. Ethylene 'lliiourea Complex inMixture Samples of cotton fabrics were treated as in Example 1 withaqueous solutions of 0.2% silver-ethylene thiourea nitrate complexes(1:4 mole ratio) and 2.5% of a polyfun-ctional reactive acrylic emulsioncopolymer of 95% ethyl acrylate and 5% N-methylol acrylamide. Thedifferent acid catalysts listed below were used to facilitate theheat-cure of the mixture. The results of antibacterial tests were asshown in the table below:

Antibacterial Ratings and Halo in mm.

, Catalyst Used Initial After 20 Soap and Chlorine Washes Excellent, 2.0Poor, 0.0. Excellent, 2.0 Excellent, 0.0. Excellent, 0.5".-. Excellent,1.0.

Excellent, 20 Very good, 0.0. Excellent, 2.5. Good, 0.0.

Excellent, 3.0 Excellnt, 0.0.

These clearly show the influence of the second component polyfunctionalcompound in fixing the silver compound on the fabric.

' Example 6 A variety of textile fabrics were impregnated with about anequal Weight of a solution containing 0.3% of silverethylene thioureanitratecomplex (1:4 mole ratio), 1.5% dimethylol: ethylene urea, 7.5% ofthe reactive acrylic copolymer identified in Example 5, and 1% catalyst,MgCl -6H O. The fabrics were then dried for 10 minines at 250 F. Theresults of antibacterial tests are shown in the table below:

Antibacterial Ratings and Halo in mm.

Silver-ethylene thiourea nitrate complex,

1:4 mole ratio 0.2 Emulsion copolymer of 95 parts ethyl acrylate and 5parts N-methylol acrylamide 5.0 Catalyst-NH Cl 0.3 (C):

Silver-ethylene thiourea nitrate complex,

1:4 mole ratio 0.2 Vinyl cyclohexane dioxide n 2.0

Emulsion copolymer of 95 parts ethyl acrylate and 5 parts glycidylmethacrylate 5.0 CatalystNH Cl 0.

The fabrics were padded through these treating baths, dried 5 minutes at250 F. and cured 5 minutes at 300 F. The fabrics were then tested forchlorine resistance by the AATCC chlorine resistance test (see 1960Technical Manual, page 123, Test Method 92l958). The tensile strength ofthe fabrics before and after chlorine test are given below:

Strip Tensile, Lbs/In.

Initial After Chlorine Test Sample A 40 0 52 44 Sample 0...- 57 53 Theseresults clearly show that the compositions of this invention producechlorine resistant finishes.

The improved capacity of the invention to provide detergent resistanceand light fast finishes is illustrated in the following example.

- Example 8 Samples of cotton fabric were treated as above with:

Percent (D):

Dimethylol silver-ethylene thiourea nitrate complex, 1:4 mole ratio 0.2CatalystNH Cl 0.3 Dimethylol ethylene thiourea 4.8 (E):

Silver-ethylene thiourea nitrate complex,

1:4 mole ratio 0.2 Emulsion copolymer of 95 parts ethyl acrylate and 5parts of N-methylol acrylamide 5.0 CatalystNH Cl 0.3

After curing as above, the whiteness of the fabrics was measuredinitially, after 20 alkaline detergent washes Fabricl e YP Initial-After 20 Detergent and after the washes and 20 hours light exposure inthe Washes FadeOmeter. The results are shown below:

G d 00 55 Spun Acrylic Excellent, 3.0... 00 Perce twh-tenes SpunTriacetate, Excellent, 3.0. Good; 0.0. n 1 s Spun Polyester" Excellent,2 0 Good, 0.0. Spun Polyamide. Excellent, 2 Excellent, 0.5. Initial 2OWashes Washes Spun Acetate- Excellent, 4 Excellent, 1.5. then Light WoolFlanneL. Excellent, 2.5. Very good, 0.0.

, gntrelategi Fabric 80 80 80 m e 80 7 A particular advantage achievedby the invention is the g g E 80 $2 capacity to resist chlorme bleachesand this is an important distinction over the prior art as isillustrated by the materials which follow.

Example 7 Samples of cotton fabrics were treated as follows from aqueousmedia:

Catalyst-NH Cl 0.3

It is desirable to improve the storage stability of the solutions anddispersions which are presently employed and to enhance the launderingand light resistant properties which are obtained upon elevatedtemperature cure after application of the treating composition to the faric. This is achieved by partially prereacting the metal complex and thepolyfunctional compound as by a heatblending operation. As heat-blendingproceeds, water solubility or dispersibility diminishes and it is merelynecessary to stop the prereaction, by discontinuing the application ofheat, before the solution or dispersion contains particles ofgelatinized material. The prereacted or heatblended materials haveessentially the same properties reported hereinbefore and thesematerials are illustrated by the prereaction product of silver-ethylenethiourea nitrate complex (1:4 mole ratio) with tris methoxymethylmelamine (Solution 2 of Example 3). This aqueous solution is prereactedby heating the solution to just below its boiling point.

Example 9 430 grams of an 80% water solution of tris methoxymethylmelamine, 20 grams of silver-ethylene thiourea nitrate (l :4 ratio) and50 grams of ethylene thiourea (excess) were reacted together forone hourat 65 C, A clear pale yellow viscous product was obtained which waswater soluble.

5% of this product was diluted with 94% water to which Was added 1% MgCl6H O as catalyst. This solution was padded onto cotton print cloth,dried 5 minutes at 250 F. and cured 5 minutes at 300 F. Then the clothwas washed 20 times in soap and sodium hypo chlorite washing solution.Even after 20 washes, the sample gave a rating of excellent and 1.0 mm.halo in the antibacterial test.

The prepolymer products of the invention may be used alone or inadmixture with any of the polyfunctional compounds or resins referred tohereinbefore.

A wide variety of compounds are known to be useful as acidic catalystsfor effecting the heat conversion of amino-plasts and similarpolyfunctional compounds as involved in this invention. Preferredclasses of such cata lysts include water-soluble acidic metal salts,watersoluble amine salts and water-soluble acids. Advantageously, thewater-solubility of such materials should be at least 1 part in 100parts of water and preferably, at least 10 parts in 100 parts of water.

Examples of suitable catalysts include free acids, e.g., hydrochloric,citric, phthalic and tartaric acids, acid-reacting metal salts, e.g.,zinc chloride, zinc nitrate, zinc fiuoroborate, magnesium chloride, andacid-reacting salts of ammonia or amines, e.g., ammonium silicofluoride, diamm-onium acid phosphate, monoethanolamine hydrochloride andthe like.

The new metal containing treating compositions of the invention may beused in conjunction with many of other known finishing agents such aswater-repellent or waterproofing compounds, polyethylene finishes,cationic softeners, plasticizers and lubricants, coating resins,coloring agents, silicones, sizing materials, e.g., starches and gums,and other agents normally used in the finishing of fibrous materials.

The invention is defined in the claims which follow:

We claim:

1. A microbiocidal composition adapted, when deposited upon fibroussubstrates and cured at elevated temperature, to render said substratesdurably resistant to attack by fungus and bacteria consistingessentially of:

(a) organo-metallic coordination complex of a biocidal metal havingcoordination properties with heterocyclic compound having the formula:

wherein R is a radical selected from the group consisting of hydrogen,hydoxyl and alkyl, alkoxy and alkoxyalkyl radicals containing from 1-6carbon atoms, and R is selected from the group consisting of a linkingbond and the divalent methylene radical; and

(b) compound containing a plurality of functional groups capable ofreacting with the NH groups of said complex to produce a Water-insolublereaction product.

2. The microbiocidal composition of claim 1 in which the molar ratio ofmetal to heterocyclic compound in said complex is in the range of from1:1 to 1:10.

3. The microbiocidal composition of claim 2 in which the weight ratio ofsaid complex to said compound containing a plurality of functionalgroups is in the range of from 1:50 to 2:1.

4. The microbiocidal composition of claim 3 in which said biocidal metalis selected from the group consisting of silver, copper and zinc.

5. The microbiocidal composition of claim 1 in which said heterocycliccompound is ethylene thiourea.

6. The microbiocidal composition of claim 1 in which the functionalgroups of said compound containing a plurality of functional groups areselected from the group consisting of oxirane, methylol, aldehyde,ethylene imine, aziridinyl, vinyl and quaternary ammonium.

7. The microbiocidal composition of claim 1 in which the functionalgroups of said compound containing a plurality of functional groups aredevoid of active hydrogen reactive with chlorine.

8. An aqueous microbiocidal composition adapted, when deposited uponfibrous substrates and cured at elevated temperature, to render saidsubstrates durably desistant to attack by fungus and bacteria consistingessentially of:

(a) organo-rnetallic coordination complex of a biocidal metal havingcoordination properties with heterocyclic compound having the formula:

wherein R is a radical selected from the group consisting of hydrogen,hydroxyl and alkyl, alkoxy and alkoxyalkyl radicals containing from 1-6carbon atoms, and R is selected from the group consisting of a linkingbond and the divalent methylene radical; the molar ratio of metal toheterocyclic compound in said complex being in the range of from 1:1 to1:10; and

(b) at least one water-dispersible compound contain ing a plurality offunctional groups capable of reacting with the NH groups of said complexto produce a water-insoluble reaction product selected from the groupconsisting of oxirane, methylol, aldehyde, ethylene imine, aziridinyl,vinyl and quaternary ammonium; the weight ratio of said complex to saidcompound containing a plurality of functional groups being in the rangeof from 1:50 to 2:1.

9. The aqueous microbiocidal composition of claim 8 in which saidbiocidal metal is selected from the group consisting of silver, copperand zinc and said heterocyclic compound is ethylene thiourea.

10. The aqueous microbiocidal composition of claim 8 in which saidcompound containing a plurality of functional groups is a monomericcompound having a functionality of at least 2.0.

11. The aqueous microbiocidal composition of claim 8 in which saidcompound containing a plurality of functional groups is an emulsioncopolymer consisting essentially of alkyl acrylate and from 1 to 25% byweight of the copolymer of acrylate having the formula:

in which R is selected from the group consisting of hy drogen and methyland X is a radical containing a functional group reactive with the NHgroup of said complex, said copolymer being dispersed in the aqueouscomposition. a

12. The aqueous microbiocidal composition of claim 8 in which saidcomposition contains from 0.05% by weight of said complex and from 1-20%by weight of said compound containing a plurality of functional groups.

13. The aqueous microbiocidal composition of claim 8 in which saidcomplex and said compound containing a plurality of functional groupsare partially heat-prereacted with one another.

14. A11 aqueous microbiocidal composition adapted, when deposited uponfibrous substrates and cured at elevated temperature, to render saidsubstrates durably resistant to attack by fungus and bacteria consistingessentially of:

(a) coordination complex of silver salt with a molar excess up to :1 ofethylene thiourea; and

(b) water-dispersible emulsion copolymer of a major weight proportion ofalkyl acrylate with from 1-25 weight percent of N-methylol acrylamide;

said composition containing from 0.055% by weight of said complex andfrom 1-20% by weight of dispersed copolymer.

15. An aqueous microbiocidal composition adapted, when deposited uponfibrous substrates and cured at elevated temperature, to render saidsubstrates durably resistant to attack by fungus and bacteria consistingessentially of:

(a) coordination complex of silver salt with a molar excess up to 10:1of ethylene thiourea; and

(b) water-dispersible emulsion copolymer of a major weight proportion ofalkyl acrylate with from 1-25 weight percent of glycidyl methacrylate;

said composition containing from 0.055% weight of said complex and from1-20% by weight of dispersed copolymer.

16. An aqueous microbiocidal composition adapted, when deposited uponfibrous substrates and cured at elevated temperature, to render saidsubstrates durably resistant to attack by fungus and bacteria consistingessentially of:

(a) coordination complex of silver salt with a molar excess up to 10:1of ethylene thiourea; and

(b) water-dispersible emulsion copolymer of a major weight proportion ofalkyl acrylate with from 1-25 weight percent of acrolein;

said composition containing from 0.055-% by weight of said complex andfrom 1-20% by weight of dispersed copolymer.

17. A light-stable and durably microbiocidal fibrous article comprisinga fiibrous substrate impregnated with the composition of claim 1, saidcomposition being heatcured in situ to a water-insoluble condition uponsaid fibrous substrate.

18. An aqueous microbiocidal composition adapted, when deposited uponfibrous substrates and cured at elevated temperature, to render saidsubstrates durably resistant to attack by fungus and bacteria consistingessentially of:

(a) organo-metallic coordination complex of a biocidal metal selectedfrom the group consisting of silver, copper and zinc with ethylenethiourea; the molar ratio of said metal to said ethylene thiourea insaid complex being in the range of from 1:1 to 1:10; and

(b) at least water-dispersible compound containing a plurality offunctional groups capable of reacting with the NH- groups of saidcomplex to produce a water-insoluble reaction product selected from thegroup consisting of oxirane, methylol, aldehyde, ethylene imine,aziridinyl, vinyl and quaternary ammonium; theweight ratio of saidcomplex to said compound containing a plurality of functional groupsbeing in the range of from 1:50 to 2: 1; said complex (a) and saidcompound (b) being partially heatprereacted with one another.

19. A light-stable and durably microbiocidal textile fabric comprising atextile fabric impregnated with the aqueous composition of claim 8, saidaqueous composition being dried and heat-cured in situ to awater-insoluble condition upon said textile fabric.

20. The article of claim 19 in which said fabric comprises cotton fiber.

References Cited by the Examiner UNITED STATES PATENTS 2,098,942 11/1937Brubaker 117-138.5 X 2,515,107 7/1950 Amick 117-138.5 3,061,469 10/1962Manowitz et al. 117138.5 3,085,909 4/1963 Gagliardi et al 117138.5

MURRAY KATZ, Primary Examiner.

WILLIAM D. MARTIN, Examiner.

T. G. DAVIS, Assistant Examiner.

1. A MICROBIOCIDAL COMPOSITION ADAPTED, WHEN DEPOSITED UPON FIBROUSSUBSTRATES AND CURED AT ELEVATED TEMPERATURE, TO RENDER SAID SUBSTRATESDURABLY RESISTANT TO ATTACK BY FUNGUS AND BACTERIA CONSISTINGESSENTIALLY OF: (A) ORGANO-METALLIC COORDINATION COMPLEX OF A BIOCIDALMETAL HAVING COORDINATION PROPERTIES WITH HETEROCYCLIC COMPOUND HAVINGTHE FORMULA: